AU616413B2

AU616413B2 - Water paint composition of resin dispersion type

Info

Publication number: AU616413B2
Application number: AU17981/88A
Authority: AU
Inventors: Sakuichi Konishi; Hideyoshi Noda; Motoyoshi Yoshikawa
Original assignee: Nippon Paint Co Ltd
Current assignee: Nippon Paint Co Ltd
Priority date: 1987-05-27
Filing date: 1988-05-27
Publication date: 1991-10-31
Anticipated expiration: 2008-05-27
Also published as: EP0317640B1; WO1988009357A1; EP0317640A4; DE3886704D1; KR960010038B1; JPS63295676A; DE3886704T2; AU1798188A; JPH0643572B2; KR890701700A; US5037865A; EP0317640A1

Description

a PCT AU-AI-17981/88 nWi4M C l afiR C09D 3/48, 5/02 (21) POT/JP88/00523 (22) [NfiME 1988445.A270 (27. 05. 88) (31) #9062-130675 (32) Afc F3 1987. 5.1278 (27. 05. 87) (33) ff Y E -9

JP

(NIPPON PAINT CO., LTD. )CJP/JP) '753i 112T~12 Osaka, (JP) (72) A M VJ115M (YOSHIKANVA, Mo toyoshi )rJP/JP) Tfff. (NODA, Hi deyoshi )CJP/JP) +19p,- MONISMI, Sakti ichi )CJP/JP) Osaka, (JP) (74) f ITJA M94iR1~ (ITOH, Takeo) Y540 p ts*Tt 7f±3Osaka, (JP) (81 A U, D E(K Ri0J4), G1 Bi4I) K R, U S.

Ait.JP.2 FEB

AUSTRALIAN

2 1DEC 1988 PATENT OFFICE 1989 (54) Title: WATER PAINT COMPOSITION OF RESIN DISPERSION TYPE (57) Abstract A water paint composition of resin dispersion type, which comprises a continuous phase composed of an aqueous medium and a water-based resin and containing dispersed therein a discontinuous phase of a wat-r-insoluble resin. The water-insoluble resin is a resin obtained by reacting a resin which contains functional groups capable of reacting with an epoxy or isocyanato group within the molecule and which is liquid at ordinary temperature wvith an epoxy compound or an isocyanate compound so that the reaction rate of the epoxy or isocyanato groups reaches 10 to 100 This paint composition shows an excellent workability in painting and can give a coat having high luster and high smoothness.

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d .4 -i i I -1- 1 Specifica' ion Resin dispersion type aqueous coating composition Field of the invention The present invention relates to an aqueous coating composition and more specifically, it concerns a resin iPierPe e4 rn b.<4 m oy)s are dispersion type aqueous coating composition -ichhi-sexcellent in application characteristics, capable of resulting a coating with far improved gloss and smoothness and is specifically useful as a top coat, an intermediate coat or an under coat for automobile bodies, electric appliance, houshold furniture and other general industrial uses, inter alia as a top coat for automobile bodies.

Background of the invention An aqueous coating composition comprising water insoluble resin microparticles uniformly dispersed in a system comprising water and an aqueous resin is being watched with keen interest in those respects of prevention of air-pollution and fire, economization in expensive, hazardous organic solvent, and capability of forming various combination of resins so as to get out the characteristic properties of the respective member.

However, such a system comprising, as film-forming components, an aqueous resin and water insoluble resin microparticles, though being excellent in applin-tion characteristics in respects of sagging and pinhole under low i I

L

i: i i e!i i:i i ~~i i i i i i -2to intermediate temperature conditions, has problem in smoothing in film-forming step and moreover, it can not give any solutions on the problem of coating failures under high temperature coating conditions.

To cope with the abovementioned problems, the present inventors have provided a coating composition comprising water insoluble resin microparticles uniformly dispersed in an aqueous resin, said water insoluble resin being prepared by the reaction of a carboxyl containing resin which is solid at room temperatures and a mono-epoxy compound or monoisocyanate compound, and a patent application was filed on it (now laid open as Kokai No. 141249-58).

According to that invention, since a highly viscous coating is obtained and coating viscosity is advantageously lowered 13 at the initial stage of baking, thus formed coating is excellent in that sagging and pinhole defects are effectively obviated. However, since the flowability is not so high, there is room for further improvements in face roughness and gloss of finished coating.

With the intention of further improvements in gloss and the like, the present inventors have also provided a coating composition comprising water insoluble resin microparticles containing a resin which is liquid at room temperatures, uniformly dispersed in an aqueous resin system and a patent application was filed on that invention (now laid open as.

Kokai No, 23330-61). Though the invention is likewise useful, the disclosed composition still has the problem such t IJ 6I' i 3 that sagging is liable to occure due to an excessive lowering in viscosity of the coating at the initial stage of baking thereof.

Under the circumstances, it has been longed for a coating composition which will satisfy the conflicting sagging and pinhole requirements in application characteristics, as well as roughness and gloss requirements in finished coating appearance.

Should a coating composition be obtained in the form of aqueous paint, containing as essential components, water, aqueous resin and water insoluble resin, those resins being selectable from variant species and the composition being able to give a coatina with excellent face roughness and gloss and free from sagging and pinhole defects, it might be !5 useful as a top coat, an intermediate coat or an under coat for automobile bodies, electric appliance, houshold furniture and other general industrial uses, and especially as a top coat for automobile bodies.

I I 2 5 i SI1 -p N-r 0, -4- The present invention provides a resin dispersion type aqueous coating composition suitable for use as a top coat, the composition comprising a continuous phase of an aqueous resin in a water medium and a discontinuous phase of water insoluble resin liquid microparticles having an average diameter of 1L or less, wherein the water insoluble resin is prepared by reacting a resin, which contains functional groups reactive with an epoxy group or an isocyanate group, with an epoxy compound or an isocyanate compound, whereby between 10% and 100% of the epoxy groups or the isocyanate groups in the epoxy compound and the isocyanate compound respectively are reacted; and if the water insoluble resin is liquid at room temperature, the water insoluble resin liquid microparticles of the discontinuous phase are uniformly dispersed in the continuous phase; or if the water insoluble resin is solid at room temperature, the solid water insoluble resin is dissolved or dispersed in a solvent and the resulting water insoluble resin liquid microparticles are uniformly dispersed in the 25 continuous phase.

As the aqueous resin, any of the known resins customarily used in coating compositions may satisfactorily be used, which may be of anionic, cationic or amphoinic nature and may be of nonionic nature, too. Most preferable 30 members are water soluble of water dispersible acryl-, alkyd-, polyester-, epoxy-, urethane-, aminoplast-, and maleinized oil- resins characterized by the later defined water tolerance and surface tension of aqueous resin solution. That is, such resin should preferably have a surface tension of 1% by wieght water solution of 51 dyne/cm or less and a water tolerance, which is a measure of dilution limit for a *'xNT6 1'4S/as 23.07.91 5 water-soluble resin and is expressed herein as the water dilution factor, with respect to the stage at which exactly of the aqueous varnish of the resin are in a 100ml beaker, at the stage, following progressive dilution with deionized water, when No. 1 type can no longer be correctly r.ead through the beaker, is 4 or more.

Then the above-defined water tolerance of a resin is less than 4, there is a tendency that when added with water insoluble resin, viscosity of thus formed composition is increased and dispersion stability is ruined. When the abovesaid surface tension exceeds over the limit of 51 dyne/cm, there are the same tendencies of increase in viscosity and lowering of dispersion stability. In the actual use of such aqueous resin, when the resin in of anionic nature as acrylic resin, alkyd resin and the like, it is advantageously neutralized with a basic compound and when the resin is of cationic nature, with an acidic compound, thereby making the resin water soluble or dispersible to obtain a water a solution or dispersion of said resin, In the present invention, water insoluble resin is dispersed and contained as a discontinuous phase, in a continuous phase of such aqueous resin and water medium. j At that time, as the water insoluble resin, is used the reaction product of a resin which is liquid at room temperatures and bears in its molecule functional groups i capable of reacting with epoxy or isocyanate group, with an ii UT 0 R 1 -6epoxy compound or an isocyanate compound so as to give a reaction rate of the epoxy or isocyanate group contained in the compound of 10 to 100%.

The abovementioned resin which is liquid at room temperatures may preferably have an acid value of 100 or less and a number average molecular weight of 1,000 100,000. The species are optional as, for example, acryl resin, alkyd resin, polyester resin, epoxy resin, aminoplast resin, acryl modified alkyd resin, acryl modified polyester resin and the like.

Examples of functional groups contained in the molecule of said liquid resin, which are reactive with an epoxy group, are carboxyl group, amino group, amide group, mercapto group, sulfonic acid group (or its salt), isocyanate group, lactone group and the like.

15 Examples of functional groups reactive with an isocyanate group are carboxyl group, hydroxyl group, amino group, amide S" group, sulfonic acid group (or its salt), epoxy group, imino o• group, mercapto group, oxime group and the like.

As the epoxy compound to be reacted with the abovementioned 20 liquid resin, mention is made of the following.

That is, as a monoepoxy compound, there are such members as, for example, olefine oxide, octylene oxide, butyl glycidyl ether, glycidyl methacrylate, p-t-butyl benzoic acid glycidyl ester, acryl glycidyl ether, glycidyl ester of tcarboxylic acid Cardula E, trademark of Shell Chem.), styrene oxide, phenyl gly-'dyl ether, p-butyl phenol S gAglycidyl ether, cresyl glycidyl ether, 3-pentadecyl phenyl 0* 1 411i 7 glycidyl ether, cyclohexene vinyl monoxide, dipentene monoxide, Gf-pinene oxide, glycidol and the like. Examples of polyepoxy compounds are Epicoat 808 (Shell Petroleum Oil Epicoat 1001 (Shell Petroleum Oil Co.) and other similar bisphenol type compounds; Chissonox CX-221 (Chisso cyclic oxirane type compound), Epicron 705 (Dainippon Ink. glycidyl ether type compound), glycidyl ester type compound and other similar alicyclic compounds; DER 736 (Dow Comp., (poly) glycol ether type compound) and other similar acyclic aliphatic compounds; Epicron 200 (Dainippon Ink and other similar polycarboxylic acid ester type compounds; Epicron 145 (Dainippon Ink and other similar halogenide type compound; Aminoglycidyl type compound; resorein type compound.

Examples of isocvanate compounds to be reacted with the abovementioned liquid resin are monoisocyanate compunds; as ethyl isocyanate, phenyl isocyanate and other alkyl or aromatic isocyanates, aromatic diisocyanates; as tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, aliphatic diisocyanates; as hexamethylene diisocyanate.

In reacting the abovementioned liquid resin with the epoxy compound or isocyanate compound, gelation is liable to occure when polyepoxy or polyisocyanate compound and/or i f/ 8 monoepoxy or monoisocyanate compound is used with the liquid ii resin whose acid equivalent is higher than the number average molecular weight thereof or when polyepoxy or polyisocyanate compound is used with the liquid resin whose acid equivalent is lower than the number average molecular weight.

Therefore, preference is given to the use of monoepoxy or monoisocyanate compound.

As to the amounts of epoxy compound or isocyanate compound used in the reaction with the aforementioned liquid resin, it is preferred to select in a range of 0.1--1.5 times the equivalent weight, and most preferably 0.1~1.4 times the equivalent weight. This is because if the epoxy compound or isocyanate compound is less than 0.1 times the equivalent weight, there is no noticable modification effect, and if the said amount is more than 1;5 times the equivalent weight, an amount of unreacted product remain in the system, causing various undesired effects as bad appearance, tackiness and the like at the film-forming stage.

The liquid resin and the epoxy compound or isocyanate compound are reacted in the following way. Y j That is, the liquid resin is used in the form of resinous varnish originally obtained in the preparation thereof, or said liquid resin may be dissolved in a solvent to provide a; solution thereof.

To this varnish or solution, added an optional catalyst i amines, organo phosphorus compounds, and the like) and Ii K\ i

I

9 then the abovementioned epoxy compound or isocyanate compound and the mixture is reacted at 100r220 0

C,

preferably 120-170°C, for 15 minutes^ 5 hours, preferably minutes-^3 hours, and the formed resin is separated.

Thus obtained resin is, when it is liquid at room temperatures, directly used as it is, or dissolved or dispersed in a solvent to get a resinous liquid. When it is solid at room temperatures, it is dissolved or dispersed in a solvent to obtain a resinous liquid, too. If desired, pigments, crosslinking agents, catalysts, dyestuffs, plasticizers and other coating additives may be dissolved or dispersed in said resinous liquid.

In this invention, thus prepared resinous liquid is then uniformly dispersed as fine liquid particles having an average diameter of I, or less, in water-aqueous resin system. At that time, mixing may be advantageously carried out by using a conventional coating-use mixer.

The present coating composition thus obtained is excellent in storage stability, as, for example, at 40'C for 1 month or more. When applied on a substrate, there is no fear of troublesome sagging in contrast to a conventional coating composition, because, despite of having a fairly low viscosity of the freshly made coating, the decrease in viscosity of the coating at the initial stage of baking is maintained in a comparatively low level. Furtheremore, i' flowability of coating composition is likewise excellent and if desired, it is able to control the baking temperature so i

I

A L1 f dl 1 10 as to give an enough time for flowing of the composition, thereby ensurig a coating with far smooth surface.

Thus, the control of coating viscosity is easily and advantageously done in the film-forming process. Therefore, it is able to get a coating with excellent gloss and face roughness, by the adoption of the present coating composition, without the fear of undesired sagging and ,-ith good operational easiness (Maximum film thickness without sagging at elevated temperatures is increased to the extent of at least 10- 30,u as compared with those of the conventional coating compositions). For these working effects, the present coating cormposition is specifically useful as a top coat for, inter alia, automobile bodies, electric appliance and the like.

The invention shall be now explained in the following Examples and Comparative Examples. Unless otherwise being stated, all parts and are by weight.

As resinous liquids, the following were used.' Synthesis of Resinous liquids Reference Example 1 (resinous liquid Into a flask, were placed 125 parts of a solution of acrylic acid having an acid value of 10.0, a hydroxyl value of 70 and a number average molecular weight of 2,500, in xylene (solid content 80%) and to this, were added 2.5 parts of phenyl glycidyl ether (Nippon Yushi Epiol P) and 0.4 part of dimethyl ethanol amine (catalyst) and the i f i l

*,V

11 combined mixture was reacted, under stirring, at 130°C for 3 hours to obtain a resinous liquid the resin contained being liquid at room temperatures.

Reference Example 2 (resinous liquid Into a flask, were placed 125 parts of the same acrylic resin-xylene solution as used in Reference Example 1 and to this, were added 1.9 parts of hydroquinone diglycidyl ether and 0.4 part of dimethyl ethanol amine and-the combined mixture was reacted under stirring at 130°C for 2 hours to obtain a resinous liquid the resin contained being at room temperatures.

Reference Example 3 (resinous liquid Into a flask, were placed 120 parts of a solution of polyester resin having an acid value of 55, a hydroxyl value of 0 and a number average molecular weight of 4,000, in Solvesso 100 (aromatic hydrocarbon solvent) (solid content To this, were added 7.15 parts of butyl glycidyl ether and 0.5 part of dimethyl benzyl amine and the combined mixture was reacted, under stirring, at 150*C for 1 hour to obtain a resinous liquid the resin contained being liquid at room temperatures.

Reference Example 4 (resinous liquid Into a flask, were placed 120 parts of the same polyester resin-Solvesso 100 solution as used in Reference Example 3. To this, were added 10.0 parts of phenyl isocyanate and 0.8 part of dibutyl tin laurate and the i combined mixture was reacted, under stirring, at 150 0 C for 4 ~ANT ji microparticles of the discontinuous phase are uniformly dispersed in the continuous phase; or if the water insoluble resin is solid at room temperature, the solid water insoluble resin is dissolved or dispersed in a solvent and the 12 hours to obtain a resinous liquid the resin contained being liquid at room temperatures.

Reference Example 5 (resinous liquid The same acrylic resin-xylene solution as used in Reference Example 1 for the synthesis of resinous liquid (1) was used, as it was, as resinous liquid Example 1 t A coating composition was prepared by mixing the resinous liquid of Reference Example 1 and aqueous resin varnish shown in Table 1, in solid weight ratio ot 37:100, at room temperature and stirring the same until a uniform composition was obtained.

Example 2~8 and Comparative Example 1 Using the resinous liquids of the abovesaic Reference Examples and aqueous resin varnishes shown in Table 1 each in the weight ratio as given in Table 2 and following the procedures of Example 1.

Each coating compositin obtained in Examples 18-0 and Comparative Example was diluted with deionized water to a Ford Cup #4 viscosity of 30 seconds and thus prepared diluted composition was applied by spraying onto a steel plate. After setting for 5 minutes, the coated plate was baked at 150 0 C for 15 minutes to obtain a crosslinked film. Test results with thus coated plate were shown in i Table 2.

-il K

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'Ii Table 1 Water soluble resin varnishes Varnish resin *1 water *2 surface acid hydroxyl neutra- neutra- resin tin oil species tolerance tension value value lizing lization solid length (times) (dyne/cm) base rate (wt%) alkyd 10< 42 55 36 *3 80 30 1360 43 resin DMEA [21 maleinized 10< 46 62 61 DMEA 80 30 1300 lineseed oil polyester 5 48 10 100 DtIEA 100 30 1500 resin acryl 104 40 69 60 DMIEA 100 30 7000 resin *1 water tolerance 5g varnish are weighed in 100ml beaker and gradually diluted with an increasing amount of deionized water. Water dilution limit wherein No. 1 type can no longer be correctly read through the beaker, is determined and expressed in terms of water tolerance *2 surface tension measured by using CB-VP type Surface tension meter manufactured by Kyowa Kagaku, with 1 wt% (solid) aqueous solution of the test varnish *3 DMEA dimethyl ethanol amine Table 2 Coating compositions and test results Comp.

Exam.

1 2 3 5 6 7 8 1 resinous liquid aq. resin varnish [4] resin aq. resin 37 3 3 37 37 3 37 3 3 S00 0 0 0o 10 00 10 liquid/ varnish /100 100 100 100 100 100 100 100 100 (solid wpight max. film thickness causing no sagging (c 60 70 65 -5 75 75 60 60 max. film thickness causing no pinholes 50 50 50 50 50 50 60 50 Blister resistance after 15 days good good good good good good good good good after 30 days good good good good good good good good good storage duration (days) of the coating composition at

Claims

1. A resin disptrsion type aqueous coating composition suitable for use as a top coat, the composition comprising a continuous phase of an aqueous resin in a water medium and a discontinuous phase of water insoluble resin liquid microparticles having an average diameter of i4 or less, wherein the water insoluble resin is prepared by reacting a resin, which contains functional groups reactive with an epoxy group or an isocyanate group, with an epoxy compound or an isocyanate compound, whereby between 10% and 100% of the epoxy groups or the isocyanate groups in the epoxy compound and the isocyanate compound respectively are reacted; and if the water insoluble resin is liquid at room temperature, the water insoluble resin liquid microparticles of the discontinuous phase are uniformly dispersed in the continuous phase; or if the water insoluble resin is solid at room temperature, the solid water insoluble resin is dissolved or dispersed in a solvent and the resulting water insoluble resin liquid 25 microparticles are uniformly dispersed in the continuous phase.

2. A composition as claimed in claim 1 wherein the aqueous resin is a water soluble or wcter dispersable acryl-, alkyd-, polyester-, epoxy-, urethane-, aminoplast- 30 or maleinized oil resin having a water tolerance (as herein before defined) of 4 or more and a surface tension of 51 dyne/cm or less.

3. A composition as claimed in claim 1 or claim 2 wherein the aqueous resin is neutralised prior to dispersion of the discontinuous phase in the continuous phase.

4. A composition as claimed in in any one of the preceding claims wherein the water insoluble resin has an ,S674S/as 23.07.91 o o s r ir t i j ii:; i ii i :;I a :i W :r -16- acid value of 100 or less and a number average molecular weight of 1,000 to 100,000. A composition as claimed in any one of the preceding claims wherein the functional groups reactive with an epoxy group are selected from carboxyl group, amino group, amide group, mercapto group, sulfonic acid group, isocyanate group and lactone group, and the functional groups reactive with an isocyanate group are selected from carboxyl group, hydroxyl group, amino group, amide group, sulfonic acid group, epoxy group, imino group, mercapto group and oxime group.

6. A composition as claimed in any one of the preceding claims wherein the epoxy compound is a monoepoxy compound selected from olefine oxide, octylene oxide, butyl glycidyl ether, glycidyl methacrylate, p-t-butyl benzoic acid glycidyl ester, acryl glycidyl ether, glycidyl ester of t-carboxylic acid, sytrene oxide, phenyl glycidyl ether, p-butyl phenol glycidyl ether, cresyl glycidyl ether, 3-pentadecyl phenyl glycidyl ether, cyclohexene vinyl monoxide, dipentene monoxide, a-pinene oxide, and glycidol. A composition as claimed in any one of claims S. 1-5 wherein the isocyanate compound is a monoisocyanate compound selected from ethyl isocyanate, phenyl isocyanate, Salkyl isocyanates and aromatic isocyanates.

8. A composition as claimed in any one of the preceding claims wherein the water insoluble resin is prepared by reacting the resin which contains functional groups reactive with an epoxy group or an isocyanate group with and amount of from 0.1 to 1.5 (on a weight basis) of S. 30 the epoxy compoundpor the isocyanage compound.

9. A composition as claimed in claim 8 wherein the resin which contains functional groups reactive with an Sepoxy group or an isocyanate group is reacted with the epoxy i group or the isocyanate group at a temperature of from

100-220 0 C. A composition as claimed in claim 9 wherein the resin which contains functional groups reactive with an I. 67 a 23 T 674S/as 23.07.91 -?i la Mlc&& -S -17- epoxy group or an isocyanate group is reacted with the epoxy group or the isocyanate group in the presence of a catalyst. 11. A composition as claimed in claim 10 wherein the catalyst is an amine or organo phosphorus compound. 12. A composition as claimed in claim 1 substantially as herein described with reference to the Examples. DATED this 23rd day of July 1991 NIPPON PAINT CO., LTD. By their Patent Attorneys GRIFFITH HACK CO. .:I i:; I 1~ s i) 1 u r so r s I~ ~I r r r r a I 674S/as 23.07.91t I Abstract of the disclosure A resin dispersion type aqueous coating composition comprising a continuous phase of water medium and an aqueous resin and water insoluble resin microparticles uniformly dispersed, as a discontinuous phase, in said continuous SIphase, which is characterized in that said water insoluble resin is such resin as being prepared by the reaction of a resin which is liquid at room temperatures and bears in its molecule functional groups capable of reacting with an epoxy or isocyanate group, and an epoxy compound or an isocyanate compound so as to give 10 100% reaction rate of the epoxy or isocyanate group contained in said compound. The present aqueous coating composition is excellent in its application characteristics and can give a coating with excellent gloss and smoothness. i I IPT 04 d INTERNATIONAL SEARCH REPORT International Application No PCT /JP 88 /00523 1. CLASSIFICATION OF SUBJECT MATTER (it several classification symbols apply, indicate all)E According to International Patent Classification (IPC) or to both National Classification and IPC Int.C1 4 C09D3/48, 5/02 It. FIELDS SEARCHED Minimum Documentation Searched Classificatn System IClassification Symbols IPC C09fl3/48, 5/02 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched Ill. DOCUMENTS CONSIDERED TO BE RELEVANT9 Category Citation ot Document, 11 with Indication, where appropriate, of the relevant passages 12 Relevant to Claim No, 13 A JP, A, 56-857 (Nissan Motor Co., Ltd.) 1-2 7 January 1981 (07. 01. 81) Page 1 US, A, 4312795 X JP, A, 58-141249 (Nippon Paint Co., Ltd.) 1-2 22 August 1983 (22. 08. 83) Page 1 US, A, 4528318 Sjpecial categories of cited documents: 10 IT" later document published after the International tiling date or document detining the general state of the art which Is not priority date and not in conflict with the application but cited to considered to be of Particular relevance understand the principle or theory underlying tha invention eartier document but published on or after the international 1X document ot particular relevance: the claimed Invention cannot filin datebe considered novel or cannot be considered to Involve an filin dateinventive step document which may throw doubts on priority claimls) or "Y document of particutar relevance: the claimed Invention cannot which is cited to establish the publication date of another be considered to Involve an inventive step when the document citation or other special reason ls specified) Is combined with one or more other such documents, such document referring to an oral disclosure, use, exhibition or combination being obvious to a Person akilled in the art other means document member of the same patent family document published prior to the International filing date but later than the priority date claimed IV. CERTIFICATION____________ Date of the Actual Completion of the International Search Date of Mailing of this International Search Report August 17, 1988 (17. 08. 88) September 5, 1988 (05. 09. 88) international Searching Authority Signature of Authorized Officer Japanese Patent'Office Form PCTIISA 210 (second sheet) (January 1985) To this varnish or solution, added an optional catalyst amines, organo phosphorus compounds, and the like) and 4 W.- ~j. gwfi,~i~iPCT/JP 8 8/ 00 5 23 4 jT (IP1C) Inr t. Ct' C09D3X48, 5/02 -T I PC C09D3/48, 5/02 A JP .56857R1 1-2 7. 1,9. 1 9 8 1 0 7. 0 1. 8 1) 'X1 A&US, A, 4 312 7 9 2 2. 8A. 19 83 22. 0 8. 83) X I A& US, A, 45 2 83 18 rEj bCD~ rY IV. Wi 1 7. 0 8. 8 8 05 -0;9 a im P V.A 4 W1 MO66ma4 J 7 12 12 4 PCT/1SA/210(Xi 2 (I981 PIO.A) I ft I j ~f